1. Field of the Invention
The present invention concerns a silver halide photographic material which has a hydrophilic colloid layer which is photochemically inert and contains a dye easily discolored and/or dissolved out in photographic processing steps and, more particularly, it relates to a silver halide color photographic material which is excellent in image sharpness, has high sensitivity of the blue-sensitive layer and is excellent in the coloring property of the bluesensitive layer and storage stability.
2. Description of the Prior Art
Silver halide color photosensitive material comprises three kinds of silver halide emulsion layers which are selectively synthesized so as to have photosensitivity to blue light, green light and red light, respectively, and usually develop colors of yellow, magenta and cyan, respectively, by using so-called couplers that react with oxidation product of an aromatic primary amine developer to form a dye.
Couplers used in this case are preferably those having desirable coloring property having a coupling rate as high as possible and providing high color density within a restricted time. Further, it is demanded that all of the color developing dyes show less side absorption.
On the other hand, it is required for the formed color photographic images to show satisfactory storage stability under various conditions.
Among them, yellow couplers excellent in coloring property and having high activity are known as disclosed in Japanese Patent Application (OPI) No. 229029/85 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application").
However, even if such an excellent coupler is used, when a multilayer photographic material is prepared, the advantageous properties of these couplers can scarcely be obtained. It has been found that this is due to the reduction of the emulsion sensitivity and developing rate owing to the dyes used in the photosensitive material.
These dyes are mainly used for the following purposes:
(1) For controlling the spectral composition of light incident on the photographic emulsion layer. (filter) PA0 (2) For preventing image blurring (halation) caused by the light transmitting through the photographic emulsion layer which is reflected at the boundary between the emulsion layer and the support, or at the surface of the support on the side opposite to the emulsion layer and again enters the photographic emulsion layer. PA0 (3) For preventing the reduction of the image sharpness (irradiation) due to the light scattering in the photographic emulsion layer. PA0 (1) To have appropriate spectral absorption depending on the use. PA0 (2) To be photochemically inert; not to give chemically undesired effects on the performance of the silver halide photographic emulsion layer, for example, reduction in the sensitivity, reduction of latent image, or fogging. PA0 (3) To be discolored or removed by dissolving in the photographic processing step leaving no harmful coloration in the photographic material after being processed. PA0 (1) A method of directly dissolving or dispersing the dyes of the present invention into the emulsion layer or hydrophilic colloid layer, or a method of dissolving or dispersing them in an aqueous solution or a solvent and then using the same for the emulsion layer or hydrophilic colloid layer They may be added to the emulsion in the form of a solution dissolved in an adequate solvent, for example, methanol, ethanol, propanol, methyl cellosolve, halogenated alcohol described in Japanese Patent Application (OPI) No. 9715/73 and U.S. Pat. No. 3,756,830, acetone, water, pyridine or the mixed solvents thereof. PA0 (2) A method of incorporating a hydrophilic polymer having the opposite electric charge to those of the dye ions in the layer as the mordant dye and localizing the dye in a specific layer due to the interaction with the dye molecules. PA0 (3) Method of dissolving the compound using a surface active agent. PA0 D- 1 N,N-Diethyl-p-phenylenediamine PA0 D- 2 2-Amino-5-diethylaminotoluene PA0 D- 3 2-Amino-5-(N-ethyl-N-laurylamino)toluene PA0 D- 4 4-[N-Ethyl-N-(.beta.-hydroxyethyl)amino]aniline PA0 D- 5 2-Methyl-4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]-aniline PA0 D- 6 N-Ethyl-N-(.beta.-methanesulfonamidoethyl)-3-methyl-4-aminoaniline PA0 D- 7 N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide PA0 D- 8 N,N-Dimethyl-p-phenylenediamine PA0 D- 9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline PA0 D-10 4-Amino-3-methyl-N-ethyl-N-.beta.-ethoxyethylaniline PA0 D-11 4-Amino-3-methyl-N-ethyl-N-.beta.-butoxyethylaniline
These layers to be colored are often composed of hydrophilic colloid and, accordingly, water-soluble dyes are usually contained in the layer for coloring them. The dye should satisfy the following requirements:
A great effort has been made by those skilled in the art for finding the dyes capable of satisfying these requirements and those dyes described below have been known. For instance, oxonol dyes having pyrazolone nuclei or barbituric acid nuclei described in British Patent 506,385, 1,177,429, 1,311,884, 1,338,799, 1,385,371, 1,467,214, 1,433,102, 1,553,516, Japanese Patent Application (OPI) Nos. 85130/72, 114420/74, 161233/80 and 111640/84, U.S. Pat. Nos. 3,247,127, 3,469,985 and 4,078,933; other oxonol dyes described in U.S. Pat. Nos. 2,533,472 and 3,379,533, British Patent 1,278,621, etc.; azo dyes described, for example, in British Patent 575,691, 680,631, 599,623, 786,907, 907,125, 1,045,609, U.S. Pat. No. 4,255,326, Japanese Patent Application (OPI) No. 211043/84, etc. azomethine dyes described in Japanese Patent Application (OPI) Nos. 100116/75, 118247/79 and British Patents 2,014,598 and 750,031; anthraquinone dyes described in U.S. Pat. No. 2,865,752; allylidene dyes described in U.S. Pat. Nos. 2,538,009, 2,688,541 and 2,538,008, British Patents 584,609 and 1,210,252, Japanese Patent Application (OPI) Nos. 40625/75, 3623/76, 10927/76 and 118247/79 and Japanese Patent Publication Nos. 3286/73 and 37303/84; styryl dyes described in Japanese Patent Publication Nos. 3082/53, 16594/69 and 28898/84; triarylmethane dyes described in British Patents 446,583 and 1,335,422 and Japanese Patent Application (OPI) No. 228250/84; merocyanine described in British Patents 1,075,653, 1,153,341, 1,284,730, 1,475,228 and 1,542,807; and cyanine dyes described in U.S. Pat. Nos. 2,843,486 and 3,294,539.
Among them, oxonol dyes having two pyrazolone rings have a nature of being discolored in a liquid developer containing a sulfite salt and have been used for dyeing photosensitive materials as useful dyes giving less undesired effects on photographic emulsions.
However, some dyes belonging to this type may have drawbacks of causing spectral sensitization in unnecessary regions of spectrally sensitized emulsions even if they give little effects on the photographic emulsions per se, or of causing reduction in the sensitivity probably because of the elimination of the sensitizing dye.
Further, along with the speed up of the developing treatment conducted in recent years, some of them may remain after the treatment. In order to overcome this problem, although the use of a dye highly reactive with sulfite ions has been proposed, this causes a defect that the stability in the photographic film is not sufficient and causes reduction with time in the density, thus failing to obtain desired photographic effects.